Process for treating an exhaust gas containing nitrogen oxides and sulfur oxides

ABSTRACT

A process is described for treating an exhaust gas containing NO x  and SO x  in which NO x  and SO x  are effectively converted into industrially useful products of NH 3 , or sulfur by use of an aqueous absorbing solution containing at least iron chelate salt and potassium sulfite.

This invention relates to a process for treating an exhaust gas containing nitrogen oxides, hereinafter referred to as NO_(x), and sulfur oxides, hereinafter referred to as SO_(x), an more precisely relates to the process in which NO_(x) and SO_(x) are effectively converted into industrially useful products of NH₃, H₂ S or sulfur by use of an aqueous absorption solution containing at least iron chelate salt and potassium sulfite.

As method for simultaneously absorbing and removing NO_(x) and SO_(x) contained in the exhaust gases, there has been known so far a process for absorbing them in an aqueous solution containing a ferrous chelate salt and an alkali sulfite to fix them in the form of imidodisulfonate, as disclosed in U.S. Pat. Nos. 3,991,161 and 3,992,508. Isolation of the imidodisulfonate thus obtained in a useful form is, however, difficult as well as disadvantageous in view of cost. It is thus desired to convert them into useful ammonia or ammonium sulfate, or into gaseous nitrogen.

In view of the above, a process is proposed, for example as in Japanese Patent Laid Open No. 108682/76, which hydrolyzes under an acidic condition of sulfuric acid an imidodisulfonate produced in the absorption solution into sulfamic acid without separating it from the absorption solution and further carries out the reaction of the sulfamic acid with nitrous acid to form nitrogen. However, hydrolysis of the imidodisulfonate at a low concentration in the absorption solution as it is without separation requires a great amount of sulfuric acid and is also disadvantageous in view of heat economy. In addition, simultaneous decomposition of a dithionate produced as by-products upon absorption requires more severe hydrolyzing conditions.

As another method, Japanese Patent Laid Open No. 125670/76 also describes a process for oxidizing a part of an alkali sulfite in the solution into an alkali sulfate, then converting the alkali sulfate into gypsum, separating the gypsum and then after the separation of imidodisulfonate from the residual filtrate converting the imidodisulfonate into ammonium sulfate through hydrolysis. However, in the process including the step of alkali sulfate-gypsum conversion the gypsum is present in the state of dissolution in the recycling solution, which is apt to precipitate as calcium sulfite scales if the alkali sulfite concentration in the solution is increased. The alkali sulfite concentration can not thus be increased and, accordingly, a ferric salt produced through oxidation upon absorption can not be reduced into a ferrous salt at a sufficient rate industrially. Then, in this case is required an additional means in which the ferric salt is reduced into the ferrous salt with use of a sulfide or the like.

The object of the present invention is to propose a process for effective treatment of the exhaust gas containing NO_(x) and SO_(x) in which a potassium sulfite used as an alkali sulfite in the absorption solution is present at a high concentration, the absorption products are crystallized to separate as potassium salts of lower solubility while reducing, at a sufficient rate, a ferric salt produced through oxidation upon absorption into a ferrous salt and, thereafter, nitrogen oxides, NO_(x), are converted into gaseous ammonia and sulfur oxides, SO_(x), are converted into hydrogen sulfide or sulfur.

Accordingly, the present invention provides a process for treating an exhaust gas containing nitrogen oxides and sulfur oxides comprising: contacting the gas with an aqueous absorption solution containing at least iron chelate salt and potassium sulfite to absorb the nitrogen oxides and the sulfur oxides into the aqueous solution; cooling the absorption solution containing absorption products of potassium imidodisulfonate, potassium dithionate and potassium sulfate to precipitate and separate the absorption products; heating the precipitate in the presence of steam to 200° to 400° C. to hydrolyze the potassium imidodisulfonate into ammonium hydrogen sulfate and potassium sulfate and at the same time to thermally decompose the potassium dithionate into potassium sulfate and sulfur dioxide gas; then adding an alkali for neutralization at a high temperature of 150° to 400° C. to generate and recover ammonia; reducing the residual potassium sulfate into potassium sulfide; and converting the potassium sulfide in an aqueous solution into hydrogen sulfide and potassium hydrogen carbonate by use of gaseous carbon dioxide.

Hereinafter, the invention is described by the accompanying drawing.

The FIGURE represents one of the process charts for carrying out this invention.

An exhaust gas 1 at a high temperature containing NO_(x) and SO_(x) is desirably cooled in a cooling tower 2 below 100° C., preferably below 80° C., so that the temperature of an absorption solution contacted in an absorption tower 3 may not exceed 70° C. This is desired since the chelating agent of an iron chelate salt in the absorption solution tends to decompose easily if the temperature of the absorption solution exceeds 70° C., and it is particularly desired to lower the temperature of the absorption solution below 60° C. in the use of ethylene diaminetetraacetate as the chelating agent. It is also desired to remove dusts, hydrogen chloride and the like contained in the exhaust gas in the cooling tower 2.

The exhaust gas 1, after cooling, is introduced in the absorption tower 3 and contacted with the absorption solution led from a pipe 4 to absorb NO_(x) and SO_(x) thereinto. The absorption solution from the pipe 4 is an aqueous solution containing 0.1 to 0.5 mol/kg, preferably 0.2 to 0.4 mol/kg of an iron chelate salt and 0.4 to 2.5 mol/kg, preferably 0.8 to 1.6 mol/kg of potassium sulfite (K₂ SO₃) and potassium hydrogen sulfite (KHSO₃). Preferred chelating agents used herein include aminopolycarboxylates such as ethlenediaminetetraacetate, nitrilotriacetate or the like.

While the solution absorbing therein NO_(x) and SO_(x) is recycled through a recycle tank 5 again into the absorption tower 3, a part of which is branched and cooled to 10° to 35° C., preferably 30° to 35° C., in a crystallizer 6 in which potassium imidodisulfonate, potassium dithionate and potassium sulfate contained in the solution as absorption products are crystallized, and then separated in a separator 7 and the filtrate is returned to the recycle tank 5. The separated crystal mixture is heated in the presence of steam to 200° to 400° C., desirably 250° to 300° C., to hydrolize the imidodisulfonate into ammonium hydrogen sulfate (NH₄ HSO₄) and potassium sulfate (K₂ SO₄) as shown by the following formula (1):

    NH(SO.sub.3 K).sub.2 +2H.sub.2 O→NH.sub.4 HSO.sub.4 +K.sub.2 SO.sub.4(1)

In the mean time, K₂ S₂ O₆ is also thermally decomposed as shown by the folloring formula (2):

    K.sub.2 S.sub.2 O.sub.6 →K.sub.2 SO.sub.4 +SO.sub.2 (2)

The gaseous SO₂ produced in the formula (2) is at least partially mixed with the exhaust gas and returned to the absorption tower.

In the above hydrolysis, while the imidodisulfonate may be hydrolyzed by heating in an aqueous solution or slurry, for the subsequent step of converting K₂ SO₄ into potassium sulfide (K₂ S), it is desired to hydrolyze it without converting into the aqueous solution. While hydrolysis in the presence of steam occurs above 100° C. and the reaction rate is increased as the temperature goes higher, thermally decomposing reaction also occurs above 400° C. together with the hydrolysis to decrease the recovery rate for ammonia in the subsequent step. Preferred reaction temperature is, therefore, between 250° to 300° C.

The thermally decomposing reaction is shown by the following formula (3):

    NH(SO.sub.3 K).sub.2 →K.sub.2 SO.sub.4 +SO.sub.2 +1/3N.sub.2 +1/3NH.sub.3                                              (3)

The crystal mixture resulting after the completion of the hydrolysis of potassium imidodisulfonate and the thermal decomposition of K₂ S₂ O₆ is then neutralized with an addition of alkali such as potassium carbonate (K₂ CO₃), potassium hydrogen carbonate (KHCO₃) or the like at a high temperature of 150° to 400° C., preferably 200° to 300° C. to generate and recover ammonia in an ammonia generator 9. While gaseous CO₂ is also produced as by-products during the addition of the alkali and admixed into the ammonia gas, it results in no troubles for ordinary use of NH₃ gas. Reaction residues are substantially composed of K₂ SO₄ and contain a little amount of unreacted K₂ CO₃.

    NH.sub.4 HSO.sub.4 +2KHCO.sub.3 →K.sub.2 SO.sub.4 +2CO.sub.2 +2H.sub.2 O+NH.sub.3                                      (4)

    NH.sub.4 HSO.sub.4 +K.sub.2 CO.sub.3 →K.sub.2 SO.sub.4 +CO.sub.2 +H.sub.2 O+NH.sub.3                                       (5)

K₂ SO₄ formed in the above reaction (1), (2), (4) and (5) is subsequently reduced into K₂ S in a reducing reaction furnace 10. A part of K₂ S thus obtained may be further converted into K₂ CO₃.

    K.sub.2 SO.sub.4 +4C→K.sub.2 S+4CO                  (6)

    K.sub.2 SO.sub.4 +2C→K.sub.2 S+2CO.sub.2            (7)

    K.sub.2 S+CO.sub.2 +H.sub.2 O→K.sub.2 CO.sub.3 +H.sub.2 S(8)

The reducing reaction may be conducted by previously incorporating carbon as a reducing agent, for example, coal, cokes, petroleum pitch, petroleum cokes or the like. In the use of coal as the reducing agent, K₂ SO₄ is mainly converted into K₂ S and K₂ CO₃ results in about 10 mol% at a temperature 900°-1000° C. The ratio of K₂ CO₃ can be increased to about 40 mol% at a reaction temperature of 800°-900° C. The ratio of K₂ CO₃ can further be increased in the use of a reducing gas such as CO, H₂ or the like. The off-gas discharged from the reducing furnace 10 is returned to the cooling tower 2 after combustion.

K₂ S and K₂ CO₃ formed in the reducing reaction are dissolved in water or a solution discharged from a below-mentioned H₂ S release tower 14 in a dissolution tank 11, thereby to make an aqueous solution, and there are removed insoluble products derived from the reducing agent in a separator 12.

Thereafter, K₂ S is converted into H₂ S and KHCO₃ using CO₂ gas. While H₂ S can be obtained by directly introducing CO₂ gas to the K₂ S solution, H₂ S concentration obtained in such a way is 10-30% by volume and the remaining portion is CO₂ gas. Consequently, this is not desired industrially since it requires a great amount of CO₂ gas. Combustion exhaust gas may be used and can ensure to provide a sufficient amount of the gas but it further lowers the concentration of H₂ S and brings O₂ into H₂ S gas. Thus, the combustion exhaust gas is not applicable to production of sulfur through Claus reaction.

For obtaining H₂ S gas at a high concentration without containing O₂, the following procedures may be taken.

A partial absorption of CO₂ gas into the K₂ S solution is at first conducted in a preliminary CO₂ absorption tower 13 until K₂ S is substantially converted to KHS without generation of gaseous H₂ S. The combustion exhaust gas with SO_(x) gas removed can be employed as the CO₂ gas source, but it may partially be replaced with the below-mentioned off-gas from a CO₂ absorption tank 15.

Absorbing reaction formula:

    K.sub.2 S+CO.sub.2 +H.sub.2 O→KHS+KHCO.sub.3        (9)

    K.sub.2 CO.sub.3 +CO.sub.2 +H.sub.2 O→2KHCO.sub.3   (10)

If the preliminary CO₂ absorption tower 13 is operated at a pH value of about 10.5, CO₂ can be absorbed with no substantial H₂ S release. H₂ S released slightly is burnt and returned to the cooling tower 2. All of the K₂ S is reduced into KHS and about one-half of the coexistent K₂ CO₃ is reduced to KHCO₃. The operation temperature is set at 30° to 80° C., preferably 40° to 60° C.

The KHS solution thus obtained is then fed to a H₂ S release tower 14. By feeding the below-mentioned filtrate obtained after separation of KHCO₃ crystals in a separator 16 optionally incorporated with a part of KHCO₃ slurry obtained from the CO₂ absorption tank 15 simultaneously and externally heating them by means of steam or the like to raise the solution temperature above 80° C. and below boiling temperature, H₂ S gas is produced through the following reaction:

    KHS+KHCO.sub.3 →K.sub.2 CO.sub.3 +H.sub.2 S         (11)

The following side reaction also occurs partially:

    2KHCO.sub.3 →K.sub.2 CO.sub.3 +CO.sub.2 +H.sub.2 O  (12)

The partial pressure P_(H).sbsb.2_(S) of H₂ S and the partial pressure P_(CO).sbsb.2 of CO₂ are represented by the following relation and H₂ S can be obtained in a high concentration of above 70% of H₂ S conc. by suitably adjusting the concentration ratio for KHS and KHCO₃.

    P.sub.H.sbsb.2.sub.S /P.sub.CO.sbsb.2 ∝[KHS]/[KHCO.sub.3 ]

H₂ S thus obtained may be oxidized in a Claus reactor 17, as required, into sulfur (S). Air may be used as an oxidizing agent therein but a part of SO₂ issued upon previous thermal decomposition of K₂ S₂ O₆ maybe used. A part of the solution after releasing H₂ S is used for the dissolution of K₂ S and the remaining part of the solution is blown with CO₂ gas in the CO₂ absorption tank 15, by which K₂ CO₃ is converted into KHCO₃.

    K.sub.2 CO.sub.3 +CO.sub.2 +H.sub.2 O→2KHCO.sub.3   (13)

While the CO₂ gas used in the above reaction can be supplied basically by the use of CO₂ gas generated upon the below-mentioned dissolution of KHCO₃ crystals in the absorbing solution, if it is insufficient, the combustion exhaust gas with SO_(x) removed can be used. Since KHCO₃ has a relatively low solubility, it forms slurry in the course of CO₂ gas absorption. The KHCO₃ slurry is partially or wholly sent to the separator 16 to separate KHCO₃ crystals therefrom.

The filtrate from the separator 16 is fed as the KHCO₃ source to the H₂ S release tower 14 and, if it is insufficient for the required amount of KHCO₃, a part of the KHCO₃ slurry is also fed together.

A small amount of K₂ S₂ O₃ is generated as by-products in the reducing reaction of K₂ SO₄ and, in the use of combustion exhaust gas with SO_(x) removed for CO₂ gas supply, K₂ S is partially oxidized into K₂ S₂ O₃ by O₂ contained in the combustion exhaust gas, which is gradually accumulated in the solution of the H₂ S release step. Since K₂ S₂ O₃ has an extremely high solubility, it can not be separated with ease from the absorption solution after it has once been incorporated therein. Accordingly, the solution discharged from H₂ S releasing step, for example, the filtrate after separation of KHCO₃ in the separator 16 is partially extracted and returned to the reducing furnace 10 to decompose and reduce K₂ S₂ O₃ into K₂ S, so that K₂ S₂ O₃ may not incorporate in KHCO₃ crystals as much as possible.

A portion of the separated KHCO₃ crystals is fed to a NH₃ generator 9 and the remaining portion is dissolved into the absorption solution and kept at predetermined K⁺ concentration and pH value. It is desired to introduce CO₂ gas generated in this course to the CO₂ absorption tank 15 for use.

    KHSO.sub.3 +KHCO.sub.3 →K.sub.2 SO.sub.3 +CO.sub.2 +H.sub.2 O(14)

Through the foregoing procedures, NOx and SOx contained in the exhaust gas can be converted into ammonia and hydrogen sulfide or sulfur.

Since K₂ SO₃ can be used at a high concentration in the absorptive solution according to this invention, the concentration of a ferrous salt in the absorptive solution can be kept high to enable the effective NOx absorption. Moreover, the absorption products can be converted into NH₃ and H₂ S or S valuable in use.

EXAMPLE STEP OF ABSORBING NO_(x) AND SO_(x) INTO ABSORPTION SOLUTION FOLLOWED BY SEPARATING NH(SO₃ K)₂,K₂ S₂ O₆ AND K₂ SO₄

To an absorption tower of 15×15 cm² in square and 8 m in height, were fed an exhaust gas of the following composition at 150 NM³ /hr. and an absorption solution of the following composition at 1.7 t/hr. The absorption rate of SO₂ is 98% and the absorption rate of NO is 81% in the period of from 5 to 100 hours.

    ______________________________________                                         Gas composition:                                                               SO.sub.2            2600 ppm                                                   NO                  180 ppm                                                    O.sub.2             4%                                                         N.sub.2             balance                                                    temperature         70° C.                                              Absorption solution composition:                                               Fe-EDTA             0.225 mol/kg                                               K.sub.2 SO.sub.3    0.95 mol/kg                                                pH                  6.5 (adjusted by K.sub.2 CO.sub.3                                              addition)                                                  temperature         55° C.                                              ______________________________________                                          (The amount of the absorption solution in the absorption system is 250         kg.)                                                                     

In the course of the above gas absorption, a portion of the absorption solution was extracted at 75 kg/hr. from the tank and cooled to 35° C. Then, the crystallized potassium salt was separated and well washed with cold water. The filtrate and washing water were incorporated with K₂ CO₃ and returned to the absorption solution tank for recycling use. The separated crystals amounted to 198 kg (dry amount) after 100 hour's operation. The crystals were a mixture of 146 kg of K₂ S₂ O₆, 23 kg of NH(SO₃ K)₂ and 29 kg of K₂ SO₄. The amount of EDTA in the absorption solution after 100 hours, when analyzed on back Ca titration, was found to be 0.224 mol/kg.

STEP OF HYDROLYZING NH(SO₃ K)₂ TO GENERATE NH₃ GAS AND SIMULTANEOUSLY DECOMPOSING K₂ S₂ O₆

19.8 kg of crystal mixture separated in the above-mentioned step was externally heated in a hydrolyzer under an atmosphric pressure in the presence of steam to an inside temperature of 300° C. in order to hydrolyze NH(SO₃ K)₂ and to thermally decompose K₂ S₂ O₆. After 30 minutes, the mixture was found to be 14.9 kg of K₂ SO₄, 0.91 kg of NH₄ HSO₄ and 0.3 kg of NH(SO₃ K)₂, and 1.37 NM³ of SO₂ gas was generated during the course of the hydrolysis. The hydrolyzates thus obtained were then transferred into an ammonia generator, incorporated with 2.00 kg of KHCO₃ in order to neutralize the produced NH₄ HSO₄ and externally heated to an inside temperature of 280° C. under stirring. Upon analysis for the contents 30 minutes after, a mixture containing 16.2 kg of K₂ SO₄, 0.18 kg of NH₄ HSO₄, 0.20 kg of NH(SO₃ K)₂ and 0.45 kg of K₂ CO₃ was found and 0.15 NM³ of NH₃ gas and 0.37 NM³ of CO₂ gas were evolved in the course of the neutralization.

STEP OF REDUCING RESIDUAL K₂ SO₄ INTO K₂ S

A mixture of K₂ SO₄, NH(SO₃ K)₂, NH₄ HSO₄, K₂ CO₃ and coal was continuously fed in the following amount to a reducing furnace of reflection type in order to reduce K₂ SO₄ into K₂ S. The furnace was directly heated by a combustion gas of high temperature generated from a kerosene burner. The coal fed as a reducing agent was contained 75% of fixed carbon and used in the pulverized form of 100 to 200μ.

    ______________________________________                                         Amount of feed                                                                 K.sub.2 SO.sub.4     24.9 (kg/hr)                                              NH(SO.sub.3 K).sub.2 0.3 (kg/hr)                                               NH.sub.4 HSO.sub.4   0.3 (kg/hr)                                               K.sub.2 CO.sub.3     0.7 (kg/hr)                                               coal                 9.2 (kg/hr)                                               ______________________________________                                    

The fed solids were melted into a liquid of low viscosity, while foaming, in about 10 minutes. The temperature of the solution was set to about 950° C. The resulted molten solution was flown out from the furnace and cooled to solidify under N₂ atmosphere. The solid thus obtained amounted to 17.6 kg/hr. and had the following composition:

    ______________________________________                                         K.sub.2 S     77.5% by weight                                                                (water insoluble content; 3.4%)                                  K.sub.2 CO.sub.3                                                                             13.0% by weight                                                                (water insoluble content; 3.4%)                                  K.sub.2 SO.sub.4                                                                              2.9% by weight                                                                (water insoluble content; 3.4%)                                  K.sub.2 S.sub.2 O.sub.3                                                                       3.2% by weight                                                                (water insoluble content; 3.4%)                                  K.sub.2 SO.sub.3                                                                             trace                                                            ______________________________________                                    

STEP OF CONVERTING K₂ S INTO H₂ S

The reaction products obtained in the above-mentioned step were dissolved in an amount of 17.6 kg/h into 144 kg/h of the solution issued from a H₂ S release tower described hereinafter and then made into a clear solution while removing insoluble components. This solution was fed to a preliminary CO₂ absorption tower and an off-gas issued from a CO₂ absorption tank described hereinafter was introduced at the bottom of the tower. The temperature in the tower was controlled to 40° C.

As the result, a solution (pH=10.4) containing 12% by weight of KHS, 21% by weight of KHCO₃ and 28% by weight of K₂ CO₃ was obtained. This solution was fed to the H₂ S release tower together with the feeding of 57.2 kg/h of a residual solution separated from KHCO₃ crystals described hereinafter (containing a little amount of KHCO₃ crystals). The H₂ S release tower had in its lower portion a reboiler to be heated by steam and the temperature of the solution was thereby kept to 105° C. As the result, H₂ S containing a great amount of steam and small amount of CO₂ was evolved. The gas was cooled to 30° C. and removed water therefrom through condensation to obtain 2.5 NM³ /h of H₂ S containing 0.8 NM³ /h of CO₂. 222 kg/h of solution was discharged from the H₂ S release tower and it was contained 13% of KHCO₃, 4.6% of KHS and 27% of K₂ CO₃.

The solution thus obtained was branched into two portions, 144 kg/h of which was used for the above-mentioned dissolution of the products of the reducing reaction and 78 kg/h of the remaining portion was fed to a CO₂ absorption tank. 10 NM³ /h of CO₂ gas was blown into the CO₂ absorption tank and vigorous stirring was effected. The temperature of the solution was controlled to a 30° C.

As the result, a slurry of KHCO₃ was obtained. KHCO₃ crystals were separated by a 28 kg/h of portion from the slurry and the residual solution was fed to the above-mentioned H₂ S release tower.

The off-gas containing CO₂ and H₂ S, issued from the CO₂ absorption tank, was led to the foregoing preliminary CO₂ absorption tower, and CO₂ gas was further absorbed therein. 

What is claimed is:
 1. A process for converting NO_(x) and SO_(x) contained in exhaust gas of combustion to ammonia and sulfur comprising:a first step of cooling said exhaust gas to a temperature lower than 100° C., a second step of absorbing said NO_(x) and SO_(x) in an aqueous solution at least containing an iron chelate, potassium salt and potassium sulfite, a third step of cooling said solution used in the second step and containing potassium imidodisulfonate and potassium dithionate formed by the absorbed SO_(x) and NO_(x), of separating the thus formed potassium salts by filtration as crystals and of recycling the filtrate to said second step, a fourth step of heating the thus formed and separated potassium salts to a temperature of 250° to 300° C. in the presence of steam to hydrolyze potassium imidodisulfonate to ammonium hydrogen sulfate and potassium sulfate and to thermally decompose simultaneously potassium dithionate into potassium sulfate and sulfur dioxide, a fifth step of admixing potassium hydrogen carbonate to the reaction residue of said fourth step at a temperature of 200° to 300° C. thereby neutralizing said reaction residue to evolve ammonia and of recovering said ammonia, a sixth step of reducing the remaining potassium sulfate by the addition of carbonaceous substance at a temperature of 900° to 1,000° C. into potassium sulfide, a seventh step of dissolving said potassium sulfide in an aqueous solution containing potassium carbonate followed by incorporating carbon dioxide thereby converting said dissolved potassium sulfide into potassium hydrogen sulfide, an eighth step of admixing an aqueous solution containing potassium hydrogen carbonate to the solution containing the thus formed potassium hydrogen sulfide thereby converting said potassium hydrogen sulfide into hydrogen sulfide and potassium carbonate, a ninth step of recovering said hydrogen sulfide, then of recycling a part of the residual solution containing said potassium carbonate into said seventh step and of incorporating carbon dioxide further into the other part of said residual solution containing potassium carbonate thereby converting said potassium carbonate into potassium hydrogen carbonate, a tenth step of recycling the resultant solution containing potassium hydrogen carbonate after separating the precipitated potassium hydrogen carbonate into said eighth step thereby converting said potassium hydrogen sulfide into hydrogen sulfide, and an eleventh step of producing sulfur by utilizing hydrogen sulfide obtained in said eighth step and sulfur dioxide obtained in said fourth step in the Claus process.
 2. The process according to claim 1, wherein said iron chelate potassium salt is ferrous and ferric ethylenediamine-tetraacetate or ferrous and ferric nitrilotriacetate.
 3. The process according to claim 1, wherein in said sixth step said reducing agent is a carbonaceous substance selected from the group consisting of coal, coke, petroleum pitch and petroleum coke. 